The preparation of epoxy-functional polysiloxane modified phenolic resole resins and use thereof in composites.
U.S. Pat. No. 5,864,000 to Lightbody is directed to hybrid phenolic/polysiloxane resins derived from (A) reacting a phenolic compound with (a) a siloxane polymer or (b) and aldehyde and (B) reacting the reaction product of(A)(a) with an aldehyde, or (A)(b) with a siloxane polymer to form the hybrid phenolic/polysiloxane resin. The siloxane polymer is defined as compounds having xe2x80x94Sixe2x80x94Oxe2x80x94Sixe2x80x94 groups in their structure. Suitable siloxane polymers were described as alkoxy and/or silanol functional siloxane polymers having a molecular weight of 1000 to 6000.
U.S. Pat. No. 5,319,005 to Hagiwara et al. relates to epoxy resin molding materials used for sealing electronic components such as transistors and integrated circuits. The composition comprises an epoxy resin having at least two epoxy groups per molecule and a phenolic compound having at least two phenolic hydroxyl groups per molecule such as phenol-formaldehyde resin condensates. To the epoxy resin containing phenolic compound are added a vinyl group-containing organopolysiloxane and a xe2x89xa1SiH group-containing organopolysiloxane as well as inorganic filler. The two types of organopolysiloxanes are permitted to react with one another to effect curing of the epoxy resin. The polysiloxanes form a particulate which is dispersed throughout the resin.
U.S. Pat. No. 4,853,434 to Block teaches a modified thermosetting resin comprising a reaction resin or reaction resin mixture and one or more three-dimensional crosslinked polyorganosiloxane rubbers. Suitable reaction resins include epoxy resins and condensation products of aldehydes, including formaldehyde, with aliphatic and aromatic compounds containing amine groups including urea or melamine as well as aromatic compounds such as phenol, resorcinol, xylene and the like. The compositions are prepared by dispersing polyorganosiloxane rubber particles in the thermosetting resin or mixture of thermosetting resins in the presence of a crosslinking catalyst at temperatures of from 18 to 120xc2x0 C.
U.S. Pat. No. 4,022,753 to Lohse et al. discloses the reaction products of a polysiloxane and polyphenols such as resorcinol, bisphenol A etc. (novolac resins) The resulting product is utilized as a curing agent or modifying agent for epoxy resins.
U.S. Pat. No. 5,530,063 to Nagai et al. shows organopolysiloxane compositions which are room temperature-curable and which comprise an organopolysiloxane, a polymer of a monomer having an ethylenically unsaturated double bond and an epoxy compound. Suitable curing agents and catalysts are also present in the formulation.
It is desirable to improve the toughness of phenolic resins without decreasing fire-resistance properties of composites.
Phenolic resole resins are modified with epoxy-functional polysiloxane by one of these methods: (1) reacting phenol with the epoxy-functional polysiloxane as the first step of preparation of the phenolic resole; (2) adding the epoxy-functional polysiloxane to the phenolic resole after the phenolic resole has been prepared (i.e. a blend procedure) or (3) reacting the epoxy-functional polysiloxane with resorcinol, bisphenol-A, or bisphenol-F, and then blending this phenolic functionalized silicone with a resole or reacting it with formaldehyde to make a resole.
Phenolic resole resin compositions are modified with epoxy-functional polysiloxanes. The compositions may be produced by several methods including (1) reacting epoxy-functional polysiloxane with phenol and then reacting the polysiloxane grafted phenol with formaldehyde to form a phenolic resole resin; (2) blending a pre-existing phenolic resin with the epoxy-functional polysiloxane and permitting the grafting reaction to proceed coincident with the curing/hardening of the phenolic resin and (3) reacting an epoxy-functional polysiloxane with a polyhydroxy phenolic monomer, such as resorcinol or a bisphenol, and either combining the reacted material with a pre-existing phenolic resin for curing/hardening or further treating the reacted material with formaldehyde or phenol and formaldehyde to make a silicon-modified phenolic resin.
The resulting compositions may be used to impregnate a variety of substrates, such as, but not limited to paper, glass roving or mat, carbon fiber, aramid fibers, kevlar, and nomex honeycomb.
Different types of epoxy-functional polysiloxanes may be used. The preferred epoxy-functional polysiloxane (epoxy silicone) is depicted by the right-hand formula below. The left-hand formula provides a shorthand definition. However, these formulas are illustrative only. The epoxy-functional polysiloxane may be any suitable epoxy-functional polysiloxane that provides the desired epoxy-functional polysiloxane-modified phenolic resin. 
The terms epoxy-functional polysiloxane and epoxy-functional silicone may be used interchangeably. In the definition of epoxy-functional polysiloxane, x is 1 to 100 and y is 0 to 10,000, and the ratio of x:y is typically from 1:0.5 to 1:100, preferably 1:1 to 1:10, and most preferably 1:1 to 1:5. One epoxy-functional polysiloxane available commercially is silicone Y-12940 from OSI Witco.
As stated above, any suitable epoxy-functional polysiloxane may be used. The polysiloxane may include branching points, and the epoxy-functional repeat units need not be adjacent to one another. Thus, the copolymer may be a random, alternating, or block copolymer. Other epoxy-functional polysiloxanes include, but are not limited to, the following epoxy-functional polysiloxane, where x is 0 to 1000, preferably 0 to 100, and most preferably 5 to 30. 
This polysiloxane is available commercially as OSI Witco Silicone Y-14362.
The epoxy-functional polysiloxane-modified phenolic resin may be made by several different procedures identified below as procedures #1, #2, and #3.
Procedure #1
First, phenol is reacted with the epoxy-functional polysiloxane to open the epoxy ring and form a Cxe2x80x94Oxe2x80x94C ether linkage between the phenol and the silicone molecule. Then, formaldehyde is added to form a phenolic resole resin with excess phenol and with epoxy-functional polysilxane-modified phenol.
More specifically, an epoxy-functional polysiloxane is mixed with excess phenol and a basic catalyst, such as sodium hydroxide, and heated to between about 120xc2x0 C. and about 180xc2x0 C., preferably about 140xc2x0 C., for between about 30 minutes and about 90 minutes. Subsequently, the reaction mixture is cooled to between about 45xc2x0 C. and about 75xc2x0 C., preferably about 55xc2x0 C., and formaldehyde is added. The reaction mixture is then heated to between about 65xc2x0 C. and about 90xc2x0 C., preferably about 75xc2x0 C., and held at that temperature until a desired free formaldehyde is achieved. Suitable free formaldehyde levels are generally between about 0.5 wt % and about 4 wt %.
Generally, the weight range of epoxy-functional polysiloxane to phenol is from about 100:0.1 to about 0.1:100, and the preferred range is about 5:100 to about 15:100. However, both ranges will be affected by the epoxy equivalent weight of the epoxy-functional polysiloxane.
The weight range of catalyst to phenol in the first step of the process is about 0.01 to about 10 parts of catalyst per 100 parts of phenol, preferably about 0.1 to about 2.5 parts of catalyst per 100 parts of phenol.
The mole ratio of formaldehyde to phenol is about 0.8:1 to about 3:1, preferably about 1.2:1 to about 1.9:1. A suitable catalyst, such as sodium hydroxide, may be added during the addition of the formaldehyde to promote the reaction between the phenol and formaldehyde.
The reaction scheme is illustrated below.
1. Reaction of phenol with epoxy silicone to open the epoxy ring and form a Cxe2x80x94Oxe2x80x94C ether linkage between phenol and the silicone. 
2. Addition of formaldehyde to form a phenolic resin. 
Procedure #2
An epoxy-functional polysiloxane is blended with a phenolic resole. The blend may be used to form composites and then cured with a suitable acid catalyst at low temperatures, or thermally cured with no catalyst at high temperatures.
First, a phenolic resole resin is prepared by reacting phenol and formaldehyde typically in the presence of a basic catalyst, such as sodium hydroxide, at a temperature below about 95xc2x0 C., preferably between about 45xc2x0 C. and about 85xc2x0 C. Then an epoxy-functional polysiloxane is blended into the phenolic resin.
The resulting mixture is added to a suitable substrate to form a composite and then the mixture is cured with an acid catalyst at a low temperature, about 25xc2x0 C. to about 100xc2x0 C., or cured without a catalyst at a high temperature, about 100xc2x0 C. to about 175xc2x0 C. During the cure, the epoxy-functional polysiloxane is reacted with the phenolic resin as illustrated below.
Generally, the formaldehyde to phenol mole ratio in the phenolic resole resin is about 0.8 to about 3.0, preferably about 1.2 to about 1.9 moles. The basic catalyst to phenol mole ratio in preparing the phenolic resole resin is from about 0.001 to about 0.1 moles of catalyst per mole of phenol, preferably from about 0.005 to about 0.05. The weight range of epoxy-functional polysiloxane added to 100 parts of the phenolic resole is from about 1 to about 100, preferably from about 3 to about 20.
The reaction scheme is illustrated below.
1. Reaction of phenol and formaldehyde to form phenolic resin. 
2. Blend of an epoxy-functional polysiloxane into a phenolic resin and then cure with an acid catalyst at low temperature or no acid catalyst at high temperature: 
Procedure #3
First a polyhydroxy compound, such as resorcinol, is reacted with an epoxy-functional polysiloxane at a temperature of between about 180xc2x0 C. and about 250xc2x0 C. for about 1 to about 7 hours. Then the polyhydroxy-modified epoxy-functional polysiloxane is blended into a phenolic resole. Alternatively, the polyhydroxy-modified epoxy-functional silicone is reacted with formaldehyde, or phenol and formaldehyde, to make a silicone-modified phenolic resole.
Generally, the mole ratio of epoxy-functional polysiloxane to polyhydroxy compound is from 0 to about 10 moles of polyhydroxy compound per mole of epoxy in the silicone, preferably from about 2 to about 3.
The weight range of silicone added to 100 parts of the phenolic resole is from about 1 to about 100, preferably from about 3 to about 20.
The mole ratio of formaldehyde to polyhydroxy compound is from about 0.5 to about 3.0 moles of formaldehyde per mole of resorcinol, preferably about 1.2 to about 1.9.
The weight range of phenol and formaldehyde added to make a silicone-modified phenolic resole is from 0 to about 100 parts of phenol per 1 part of silicone. Formaldehyde is further added in a molar ratio of about 0.9 to about 3.0 moles of formaldehyde per mole of phenol, preferably about 1.2 to about 1.9 moles of formaldehyde per mole of phenol.
1. Reaction of resorcinol with epoxy-functional polysiloxane. 
2. Blend with premade resole and then cure with an acid catalyst. 
3. Alternatively, further reaction of the resorcinol-modified epoxy-functional polysiloxane with formaldehyde or formaldehyde and phenol. 
Procedures #1, #2, and #3 include both the prereaction or xe2x80x9cgraftingxe2x80x9d of epoxy-functional polysiloxanes with phenol, alkyl phenols, polyhydroxy phenols such as resorcinol, polyphenol compounds such as bisphenol-A and bisphenol-F, or phenolic resoles, as well as the blending of epoxy-functional polysiloxanes into phenolic resoles, both in the reactor where the phenolic resole is manufactured and in fabricators"" tanks prior to manufacture of the composites.
The term phenol is used generically to encompass any suitable phenolic compound.
The present invention is also directed to a mixture of the compositions prepared by procedures #1, #2, and/or #3.
In general, the phenolic resins have a F:P mole ratio of about 0.8 to about 4.0, preferably about 1.0 to about 2.0, and most preferably about 1.6. The phenolic resins are preferably made using a catalyst as known in the art. Suitable catalysts include hydroxides such as sodium hydroxide, or amines such as hexamine. The phenolic resins may be made in situ or premade in a separate reactor for blending with the epoxy-functional polysiloxane. Specific resins are described in the examples.
Suitable epoxy-functional polysiloxanes include OSI Witco Y-12940 and OSI Witco Y-14362. Other epoxy-functional silicones include, but are not limited to, Dow Corning 2-8065, DC Toray Silicones BY 1-2940, ShinEtsu KF-105, ShinEtsu X-22-163A, Shin Etsu X-22-163B, and ShinEtsu X-22-163C.
Regardless of which procedure is used, the resulting epoxy-functional polysiloxane modified phenolic resin may be heat cured or cured in the presence of an acid, either added during the manufacture of the resin as a neutralizing agent, or added externally prior to curing the resin.
The epoxy-functional polysiloxane modified phenolic resins may be heat cured at a temperature above about 90xc2x0 C., preferably about 100xc2x0 C. to about 175xc2x0 C.
The acid catalyst may be any suitable acid catalyst known to those skilled in the art such as mineral and organic acids and their derivatives, such as esters and amides or acid catalysts such as those described in U.S. patent application Ser. No. 08/681,681, hereby incorporated by reference in its entirety. Specific acid catalysts include p-toluenesulfonic acid, esters of phosphoric acid, and hydrochloric acid, sulfuric acid, and their derivatives. Another suitable acid catalyst is described in Table I.
The acid catalyst is added in an amount effective to cure the epoxy-functional polysiloxane modified phenolic resins and the amount depends on the strength of the acid catalyst. For the catalyst listed in Table I, and comparable acid catalysts, the operative range is from 1 to 30 parts by weight of catalyst per 100 parts of resin, and the preferred range is from 5 to 15 parts by weight.
The phenolic component reacts with the epoxy functional group of the silicone to form a Cxe2x80x94Oxe2x80x94C bond. Some of the advantages of the three procedures include:
(1) formation of a stable chemical linkage between the silicone and the phenolic component;
(2) improved compatibility of the silicone with the phenolic network;
(3) improved reactivity of the phenolic-functionalized silicone with the rest of the phenolic matrix; and
(4) improved performance upon exposure to hot-wet conditions.
Another embodiment is directed to uncatalyzed or acid catalyzed compositions with a substrate such as paper, glass, glass cloth, carbon fiber, and aramid substrates such as kevlar or nomex to make a composite material such as a laminate, tube, pipe, honeycomb, or various molded parts by processes such as a filament winding, impregnation (prepregging), pultrusion, dipping, spraying, hand lay-up, sheet molding compound, SCRIMP, or other processes known to those familiar with the composites industry. For example, four-ply glass cloth laminates where prepared using the epoxy-functional polysiloxane modified resole of procedure #2 with 11.5 parts of the acid catalyst described in Table I.
The range for the amount of resin to be added to the substrate in the practice of the invention varies based on the process used. Generally the weight range is from about 1 to about 100 parts of resin per 100 parts of substrate. The preferred weight range again varies from process to process, but it is typically in the range of about 10 to about 50 parts of resin per 100 parts of substrate.
Generally, the reactions and blendings are practiced at atmospheric pressure, but reduced pressures to pressurized vessels may also be used.